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Adsorption, orientation and thermal decomposition of copper(II) hexafluoroacetylacetonate on rutile TiO2(110)

Mulley, J.S., Bennett, R.A. and Dhanak, V.R. (2008) Adsorption, orientation and thermal decomposition of copper(II) hexafluoroacetylacetonate on rutile TiO2(110). Surface Science, 602 (18). 2967-2974 . ISSN 0039-6028

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To link to this item DOI: 10.1016/j.susc.2008.07.026

Abstract/Summary

We have investigated the adsorption and thermal decomposition of copper hexafluoroacetylacetonate (Cu-11(hfaC)(2)) on single crystal rutile TiO2(110). Low energy electron diffraction shows that room temperature saturation coverage of the Cu-II(hfac)(2) adsorbate forms an ordered (2 x 1) over-layer. X-ray and ultra-violet photoemission spectroscopy of the saturated surface were recorded as the sample was annealed in a sequential manner to reveal decomposition pathways. The results show that the molecule dissociatively adsorbs by detachment of one of the two ligands to form hfac and Cu-1(hfac) which chemisorb to the substrate at 298 K. These ligands only begin to decompose once the surface temperature exceeds 473 K where Cu core level shifts indicate metallisation. This reduction from Cu(I) to Cu(0) takes place in the absence of an external reducing agent and without disproportionation and is accompanied by the onset of decomposition of the hfac ligands. Finally, C K-edge near edge X-ray absorption fine structure experiments indicate that both the ligands adsorb aligned in the < 001 > direction and we propose a model in which the hfac ligands adsorb on the 5-fold coordinated Ti atoms and the Cu-1(hfac) moiety attaches to the bridging O atoms in a square planar geometry. The calculated tilt angle for these combined geometries is approximately 10 degrees to the surface normal.

Item Type:Article
Refereed:Yes
Divisions:Faculty of Science > School of Mathematical, Physical and Computational Sciences
Faculty of Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:1414
Uncontrolled Keywords:TiO2(110), Organometallic, Adsorption, ALD precursor, NEXAFS, LEED, XPS, UPS, ATOMIC-LAYER-DEPOSITION, CHEMICAL-VAPOR-DEPOSITION, YTTRIA-STABILIZED, ZIRCONIA, FORMIC-ACID ADSORPTION, CU(I) VINYLTRIMETHYLSILANE, ELECTRONIC-STRUCTURE, SURFACE, TIO2, SPECTROSCOPY, SPECTRA

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